New energetic polynitro cyclic esters: ammonium, hydrazinium, and hydroxylammonim salts of polynitramines

Reaction of 2,2-dinitro-1,3-propanediol (1) with oxalyl dichloride or malonyl dichloride in refluxing ether led to the formation of cyclic dinitro-containing esters (2, 3) in very good yields. Compounds 2 and 3 were also isolated in similar yields by the treatment of 1 with oxalic acid or malonic acid in trifluoroacetic anhydride at room temperature. Nitration of 3 with fuming nitric acid resulted in the corresponding trinitro cyclic ester 4 in 70% isolated yield. Treatment of 1 with a large excess of methanolic ammonia gave impure 2,2-dinitro-1,3-diaminopropane (5). Polynitraamines, 7 and 11, were treated with aqueous ammonia, hydrazine monohydrate or hydroxylamine in methanol at room temperature to obtain their corresponding salts 8-10 and 12-14, respectively, in excellent isolated yields. All new compounds were characterized by IR, NMR spectroscopy ((1)H, (13)C, (15)N), DSC, and elemental analysis. Their energetic properties, such as impact sensitivity, detonation velocity, and detonation pressure were also determined and compared with existing energetic compounds, such as PETN (pentaerythritol tetranitrate), RDX (1,3,5-trinitro-1,3,5-triazacyclohexane), and TNT (trinitrotoluene).